DE1544447B2 - Stilbenazo reactive dyes and processes for making these dyes - Google Patents

Description

2. Fiber-reactive azo dyes according to claim 1 of formula 1, wherein X and Y are each one of the

SO ₃ H

-NH

CH = CH

SO ₃ H

Description mentioned sulfoarylaminochlorotriazine residue or mean carboxyarylamino-chlorotriazine radicals.

3. Fiber-reactive azo dyes according to Claim 2 of the formula

X-

SO ₃ H

SO ₃ H

where R is a benzene radical free of sulfonic acid groups and R _{1 is} a low molecular weight alkyl group or a hydroxyethyl group and X and Y have the meanings given in claim 2.

4. Fiber-reactive azo dyes according to claim 2 of formula 2, wherein R is a sulfonaphthylene radical and R _{1 is} hydrogen.

5. Fiber-reactive azo dyes according to any one of claims 1 to 4, the at least four sulfonic acid groups contain.

6. Fiber-reactive azo dye according to claim 3 of the formula

: N =

NH-C

C-NH

SO ₃ H

SO ₃ H

SO ₃ H

C.
Cl

The present invention relates to a process for the preparation of new, valuable azo dyes, those as free acids of the formula

45

SO ₃ H

ch = ch

SO ₃ H

correspond, where η is a whole positive number of at most 6, but preferably 1, R is a benzene or naphthalene radical which is bonded in the 1,4-position and has sulfo-, methyl-, methoxy-, acetylamino, propionylamino as substituents -, methanesulfonylamino or ureido radicals, R _{1 is} a hydrogen atom or a lower alkyl group, and X and Y are each a fiber-reactive chlorotriazinyl radical.

If one of the two fiber-reactive substituents does not contain any acidic water-solubilizing groups, so at least one and preferably two such groups must be present in the other reactive radical be. Both fiber-reactive radicals advantageously contain at least one water-solubilizing group.

Of particular interest are the dyes of the present application, which are at least four acidic water-solubilizing groups, e.g. B. contain sulfo, carboxy or sulfato groups.

The dyes according to the invention can be prepared by condensation of dyes of the formula

55

N = N-R-NH

Q "-1 H ₂ ," _ ι

in which m and η are each an integer positive number of at most 6, but preferably 1, R is a benzene or naphthalene radical bonded in the 1,4-position and Z is a hydrogen atom or a chlorotriazinyl radical, with chlorotriazines.

Suitable chlorotriazine radicals X and Z are the 4,6-dichloro-1,3,5-triazinyl radical, the monochlorotriazinyl radical, which, as a further substituent, is the residue of a thioalcohol, thioglycolic acid, or thiourea, a thiophenol, methyl, ethyl or isopropyl alcohol, glycolic acid, phenol, Chlorine or nitrophenols, a phenol carbon and

sulfonic acid, naphthol, a naphtholsulfonic acid or -NH ₂ , -NH - OH radical, the hydrazinyl, phenylhydrazinyl radical, the radical phenylhydrazine sulfonic acid, the carbamic acid of semi- or thiosemicarbazide or carbazone, the methyl, ethyl, isopropyl , Methoxyethyl, methoxypropylamino, dimethyl, diethyl, methylphenyl, ethylphenylamino, chloroethylamino, ethanolamino, propanolamino, benzylamino, cyclohexylamino, morpholinyl, piperidinyl, piperazinyl acetic acid esters, the remainder of the aminocarbonic acid esters , the aniline, N-methylaniline, toluidine, xylidine, chloroaniline, p- or m-aminoacetanilide, nitroaniline, aminophenol, nitrotoluidine, phenylenediamine, toluenediamino, anisidino, phenetidino, diphenylamino -, Naphthylamino, aminonaphthylamino, aminonaphthols, diaminonaphthalino or like / i-sulfatoethylamino, aminoethanesulfonic acid, N-methylaminoethanesulfonic acid, sulfanil, metanil, orthanilic acid, anilinedisulfonic acid, aminobenzoic acid laminmono-, di- and trisulfonic acid, aminobenzoic acid-sulfonic acid, the l-oxy-5-aminobenzoic acid and the aminonaphthalene mono-, di- and trisulfonic acid radical.

The introduction of the 2-position by the remainder of one of the aforementioned by a hydroxyl, mercapto or amino compound substituted triazine ring can be conveniently done in the manner that first the azo dye prepared by coupling with a 2,4,6-trihalogeno-1,3,5-triazine, in particular cyanuric chloride, and then converted into the dihalotriazinyl compound obtained introduces one of the abovementioned radicals by condensation in a known manner.

The starting dyes of the formula 2 can be prepared in such a way that one diazo compounds from the amines of the formula

SO ₃ H

CH = CH

NH,

SO ₁ H

Cresidine, 2,5-dimethoxyaniline, m-acetylaminoaniline, m-propionylaminoaniline, m-methanesulfonylaminoaniline, m-ureidoaniline and the like, α-naphthylamine, 6-, 7- or 8-sulfo-1-aminonaphthalene and the like.
The condensation according to the invention can be carried out in a manner known per se, for. B. in an aqueous medium with the addition of acid-binding agents such as sodium hydroxide or sodium carbonate. If Z in the starting dyes is a hydrogen atom, at least 2 moles of the compound introducing the fiber-reactive substituents are of course to be used per mole of dye; if Z is already a fiber-reactive radical, the use of at least 1 mol of the compound carrying the fiber-reactive radical is sufficient for the condensation and both fiber-reactive substituents X and Y can be the same or different in the end products.

Among the dyes thus obtained, two groups deserve special mention, namely those the formula

SO ₃ H

^χ - ^ΝΗ <Χ

SO ₃ H

CH = CH

N = N-R-N-Y

where R denotes a benzene radical which is free of sulfo and carboxy groups and is bonded in the 1,4-position, R _{1 is} a low molecular weight alkyl radical and X and Y are each a 2-chloro-4-amino-1,3,5- bonded in the 6 position mean triazine radical, the 4-amino group in both radicals being derived from an aromatic amine containing sulfonic acid groups, and those of the formula

SO ₃ H

_v .xtu _ / \ / SO, H

CH = CH

wherein X _{1 is} a nitro group, an acylamino group or a radical of the formula

- Ν —Ζ

denotes in which Z and η have the meaning given in the explanation of the formula 2, couples with amines of the benzene or α-naphthalene series which couple in the p-position and of the formula

R-NH

correspond, in which R and m have the meaning given in the explanation of the formula 2, and, in the case where X _{1 represents} a nitro or acylamino group, this is subsequently reduced or saponified in the dye obtained.

Such amines may be mentioned: aniline, N-methyl- or N-ethylaniline, Ν, / i-hydroxyethylaniline, xylidine, m-toluidine, N-methyl-m-toluidine, o-anisidine.

NH-Y

HO ₃ S

wherein X and Y each have a 2-chloro-4-amino-1,3,5-triazine radical bonded to the - NH bridge in the 6-position means, where in at least one of the two radicals the 4-amino group is different from one sulfonic acid group-containing aromatic amine derived.

The dyes obtained by the specified process are new. They are valuable dyes that for dyeing and printing a wide variety of materials, especially polyhydroxylated materials fibrous structure, such as cellulosic fabrics, both synthetic fibers, e.g. B. off regenerated cellulose or natural cellulose materials, e.g. B. pulp, linen or above all Cotton are suitable. They are particularly suitable for dyeing using the so-called direct dyeing method from a long liquor, from an alkaline, possibly highly salty, aqueous bath.

In order to improve the wet fastness properties, it is advisable to use the dyeings and prints thus obtained thorough rinsing with cold and hot water, optionally with the addition of a dispersing agent acting and the diffusion of the unfixed dye portions promoting agent to submit.

The dyes according to the invention are particularly notable for a high degree of fixation and a easy washability of the unfixed dye components and the resulting colorations through very good wash fastness and good chlorine and light fastness.

Compared to the dyes of the French patent specification 1,198,036 and the British patent specification

IO

852 120, the dyes of the present application are distinguished by better fastness in the acid hydrolysis test the end. This could be from the constitutions and the properties of the dyes mentioned Patent specifications cannot be readily derived. The one with the dyes of the present Registration achieved technical progress is therefore unexpected and surprising, the claimed new dyes are therefore inventive.

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

example

24.4 parts of the dye of the formula

H ₂ N

CH = CH

N = N

NHCH ₃

SO ₃ H

SO ₃ H

in a known manner z. B. by coupling 4-nitro-4'-aminostilbene-2,2'-disulfonic acid onto N-methylaniline and by subsequent reduction of the nitro group to the amino group with the aid of sodium sulphide can be prepared are suspended in 500 parts of water and the resulting suspension neutralized by adding sodium hydroxide. Then give a solution to the resulting solution Solution of the primary condensation product from 25.3 parts of aniline-2,5-disulfonic acid and 18.5 parts Cyanuric chloride and heats the whole thing to 40 to 50 °. During the condensation, the pH of the solution becomes kept between 6 and 7 by the dropwise addition of 2N sodium hydroxide solution. After condensation has taken place the dye is salted out with a mixture of sodium and potassium chloride, filtered off and dried. The dye thus obtained dyes cotton in reddish-tinged yellow shades.

example

25.1 parts of the dye of the formula

H ₂ N

CH = CH

N = N

NHCH ₃

SO ₃ H

SO, H CH ₃

are suspended in 500 parts of water and the resulting suspension by adding sodium hydroxide neutralized. The resulting ice-cold solution is then mixed with a solution of 18.5 parts Cyanuric chloride is added in 100 parts of acetone, and 2N sodium hydroxide solution is added dropwise the pH is kept between 6 and 7. The dye obtained in this way, which has approximately four mobile chlorine atoms contains, dyes cotton in reddish-yellow tones.

Example 3
30.2 parts of the dye of the formula

CH = CH

N = N

NH,

SO ₃ H

SO ₃ H SO ₃ H

that by coupling 4-nitro-4'-aminostilbene-2,2'-disulfonic acid to l-naphthylamine-8-sulfonic acid and produced by subsequent reduction of the nitro group to the amino group with the aid of sodium sulphide can be suspended in 500 parts of water and the resulting suspension through Addition of sodium hydroxide neutralized; at room temperature, the resulting solution of 18.5 parts of cyanuric chloride in 100 parts of acetone are added. By adding dropwise 2N sodium hydroxide solution the pH of the solution is kept between 6 and 7 during the condensation. After Condensation, the solution is mixed with 40 parts of ammonia (25%) and heated to about 3 hours 40 to 45 °. After cooling, the precipitated dye is filtered off and dried. He dyes cotton in reddish orange tones.

If in the above example the l-naphthylamine-8-sulfonic acid is replaced by the l-naphthylamine-6- or -7-sulfonic acid, this gives dyes that dye cotton in orange tones.

7 8

Dyeing instructions 2 parts of the dye obtainable according to Example 1, the free acid of the formula

/ \
Cl-C C-NH-

N N

SO ₃ H HO ₃ S

HO ₃ S

CH =

SO ₃ H

SO ₃ H

corresponds to are dissolved in 100 parts of water.

The solution is added to 3900 parts of cold water, 40 parts of trisodium phosphate and 80 parts are added Sodium chloride and goes with 100 parts of a cotton fabric in this dye bath.

The temperature is increased to 90 ° in 45 minutes, with another 80 parts of sodium chloride after 30 minutes be admitted. The temperature is kept at 90 ° for 30 minutes, then the rinsed and soaped Staining for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinses and dries.

The result is a washable and lightfast, reddish-yellow coloration.

Example 4

A solution of 37 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid, neutralized with sodium carbonate, is added to an aqueous solution of the primary condensation product of 18.5 parts of cyanuric chloride and 25.3 parts of aniline-2,5-disulfonic acid the reaction mixture for 2 hours at 20 to 25 ° by gradually adding a dilute sodium hy-SO ₃ H

hydroxide solution weakly acidic to neutral. It is then cooled to 10 ° and acidified with 30 parts of 30% strength hydrochloric acid and diazotized with a solution of 6.5 parts of sodium nitrite. To the diazo compound one adds a solution of 10.7 parts of N-methylaniline in 100 parts Water containing 10 parts of 30% hydrochloric acid.

The pH of the coupling mixture is adjusted to 3 to 4 by adding sodium acetate and the mixture is stirred, until the coupling is finished. The monoazo dye is salted out, filtered off and dissolved in 800 parts of water solved. A solution of the disodium salt from 32 parts of 2,4-dichloro-6-phenylaminol, 3,5-triazine-3'-sulfonic acid is added to this and stir the mixture for 6 to 10 hours between 50 and 60 °. It is then cooled to room temperature and left to stand for 24 hours. The precipitated dye is filtered off, washed with a 20% sodium chloride solution and dried. It dyes cotton in pure, reddish-yellow tones. Other dyes made according to the methods given by diacylation of the stilbene dyes listed in column I of the table below with the Dichlorotriazine derivatives of the amines listed in column II are available, dye cotton in the tones given in column III.

I. 1 4- (4 "-N-methylaminophenylazo) - II III 4'-aminostilbene-2,2'-disulfonic acid 1-aminobenzene-3-sulfonic acid reddish yellow 2 the same 2-carboxy-1-aminobenzene- reddish yellow 3 the same 4-sulfonic acid 1 -Methylaminobenzene- reddish yellow 4th the same 4-sulfonic acid 5 the same Aniline-oj-methanesulfonic acid reddish yellow 6th the same 3-aminobenzylsulfonic acid reddish yellow Mixture of 1-aminobenzene- reddish yellow 3-sulfonic acid with 1-amino 7th the same benzene-2,5-disulfonic acid 2-aminonaphthalene reddish yellow 8th the same 4,8-disulfonic acid 2-aminonaphthalene reddish yellow 9 the same 4,6,8-trisulfonic acid 1 -aminonaphthalene- reddish yellow 10 the same 3,6-disulfonic acid 11th the same Aminomethanesulfonic acid reddish yellow / i-sulfatoethylamine reddish yellow

409 586/360

continuation

I. 12th 4- (4 "-N-methylamino-2" -methyl- Il III phenylazo) -4'-aminostilbene- 1-aminobenzene-3-sulfonic acid reddish yellow 2,2'-disulfonic acid 13th the same 14th 4- (4 "-N-ethylaminophenylazo) - 1-aminobenzene-2,5-disulfonic acid reddish yellow 4'-aminostilbene-2,2'-disulfonic acid the same reddish yellow 15th 4- (4 "-N, ß-Hydroxyäthylaminophenylazo) - 4'-aminostilbene-2,2'-disulfonic acid the same reddish yellow 16 4- (4 "-aminophenylazo) -4'-aminostilbene- 2,2'-disulfonic acid the same reddish yellow 17th 4- (4 "-amino-2" -methylphenylazo) - 4'-aminostilbene-2,2'-disulfonic acid the same reddish yellow 18th 4- (4 "-amino-2", 5 "-dimethylphenylazo) - 4'-aminostilbene-2,2'-disulfonic acid the same reddish yellow 19th 4- (4 "-amino-" -methyl-S ^ methoxy- phenylazo) -4'-aminostilbene- the same reddish yellow 2,2'-disulfonic acid to orange 20th 4- (4 "-amino-6" -sulfonaphthyl- (l ") - azo) - 4'-aminostilbene-2,2'-disulfonic acid the same reddish orange 21 4- (4 "-amino-8" -sulfonaphthyl- (1 ") -azo) - 4'-aminostilbene-2,2'-disulfonic acid 1-aminobenzene-3-sulfonic acid reddish orange 22nd 4- (4 "-N-methylamino-2" -methyl- phenylazo) -4'-aminostilbene- l-aminobenzene-2,4-disulfonic acid reddish orange 2,2'-disulfonic acid 23 the same 2-carboxy-1-aminobenzene- reddish orange 4-sulfonic acid

Claims (1)

Patent claims:
Fiber-reactive azo dyes of the formula SO ₃ H (D N = N-R-N-Y where η is a whole positive number of at most 6, but preferably 1, R is a benzene or naphthalene radical bonded in the 1,4-position, the sulfo, methyl, methoxy, acetylamino, propionylamino, methanesulfonylamino or ureido radical may contain as substituents, R _{1 is} a hydrogen atom or a low molecular weight alkyl group, and X and Y are each one of the chlorotriazine radicals listed in the description.